Process of producing a phenolic condensation product



Patented June 23, 1925.

UNITED STATES PATENT OFFICE. I

CARNIE B. CARTER AND ALBERT E. COXE. OF PITTSBURGH, PENNSYLVANIA, AS-

SIG-NORS TO S. KARPEN & 31305., OF CHICAGO, ILLINOIS, A CORPORATION OF WEST VIRGINIA.

PROCESS OF PRODUCING A PHENOLIC CONDENSATION PRODUCT.

No Drawing.

To all whom it may concern:

Be it known that we, CARNIE B. CARTER and ALBERT E. Coxn, citizens of the United States, residing at Pittsburgh, in the county of Allegheny and State of Pennsylvania, have invented a new and useful Improve ment in Processes of Producing a Phenolic Condensation Product, of which the follow ing is a specification.

This invention relates to the production of phenolic condensation products; and the primary object is to provide a simple and practicable process for producing such prod acts by reacting upon a phenolic body with an. aldehyde dichloride. Such dichlorides are obtainable as by-products when natural gas is subjected to a chlorinating process for the purpose of obtaining, as a principal product, methyl chloride for use in the pro- 2% duction of esters, as described in our pend ing application for Letters Patent of the United States Serial No. 423,870, filed Noyember 13, 1920, which has matured into Patent.1,459,971, Jan. 26, 1923.

The various chlorinated products produced by chlorinating methane or natural gas may be separated in accordance with the method set forth in our application 583,913, filed of even date herewith.

A phenolic body, such as phenol or the cresols, may be condensed with the aldehyde dichlorides of the aliphatic series to form phenolic condensation products. For example, one of the first three members ofthe homologous series of aldehyde dichlorides may be readily condensed with phenol or cresols, by employing a suitable catalyst, such as ammonia. The first three members of this series are:

Methylene chloride, CH,C1,..

Ethylidene chloride, CI'LCHCI Propylidene chloride, CH CH CHCl Of the three substances named above, the methylene chloride reacts very readily; the ethylidene chloride reacts more slowly; and the propylidene chloride reacts still more slowlyassuming the same conditions.

Even with methylene chloride, the condensation takes place extremely slowly in the absence of a condensing agent. The ordi- Application filed August 23, 1922. Serial No. 583,914.

nary alkalies, that is, the alkaline compounds of the alkali metals or alkaline earth metals, will not serve as a condensing agent. Ammonia, however, if present in an amount suflicient to combine with the chlorine that is present in the methylene chloride will enable the condensation of an aldehyde dichloride and a phenolic body to be readily effected;

It is preferred to employ such proportions, in the first instance, as will give a largeexcess of phenol and enable a fusible phenolic condensation product to beproduced. For example, one may use the following proportions:

5 cc. of phenol.

6.4: cc. of concentrated ammonium hythis mixture and then hermetically sealed.

The tube may then be put in a heated oil bath and heated thirty minutes at 180 C.

The reaction is found to be practically com plete at the end of this time. There results a resin in the formof a viscous liquid which forms a layer at the bottom of the tube, and above this is an a ueous layer which carries ammonium chloride which is formed in the reaction. On cooling, the aqueous layer deposits crystalline ammonium chloride copiously and the resin becomes yery viscous or semi-solid in character.

Theviscous resin may be washed free of ammonium chloride by agitation or by kneading with hot or cold water, after which the excess phenol, or part thereof, may be boiled off or may be blown out at elevated temperature by means of air. The resulting viscous liquid becomes a solid on cooling to ordinary temperatures. If a portion only of the excess phenol be blown oil, the resulting resin will be hard and brittle when cold, will be fusible, and will be soluble in aqueous alkalies, alcohol, acetone, ether, etc. In fact, such a resin possesses all the properties of the fusible soluble resins prepared from phenol and formaldehyde or hexamethylenetetramine and the resin may be spond with the followlng molecular ratios:

' Phenol, 9 mols.

Ammonia, 16 mols.

Methylene chloride, 6 mols.

According to the foregoing, more ammonia is employed than 18 essential for a complete reaction of the methylene chloride. Only 12 mols. are required in fact, and the reaction proceeds smoothly to completion if only 12 mols. are used. An excess of ammonia does no harm, however, and it is practical to employ an excess to make it certain that there will be sufficient ammonia present to combine with all of the chlorine present in the reaction.

It is not essential that the ammonia be used as concentrated ammonium hydroxide, for example. As a matter of fact, it is desirable when the resin is made in large quantity to employ a more dilute solution. The condensation is accompanied by the evolution of a large amount of heat and in the case of the treatment of large masses of reacting materials, it is desirable to temper the reaction by the presence of water, which may be used advantageously and in considerable quantity.

In practice, the condensation may be performed conveniently in an autoclave. A temperature of 180 C. has been given as a suitable temperature for effecting the condensation. The condensation can be effected in the presence of ammonia at 100 C. in the course of 12 to 24 hours, however. It is desirable to employ a base as a condensing agent. However, an ammonia compound is the only reagent of an alkaline character that is of practical value. The other alkalies, that is, the ordinary alkali metal and alkaline earth metal compounds, possess no value as condensing agents in the present process. Indeed, they have a tendency to prevent complete condensation when present, even though the requisite amount of ammonia be used.

Where the reaction is carried out in an autoclave at a suitable temperature, pressure is developed in the autoclave and the pressure developed may vary ditions, that is, with the extent to the autoclave is filled with the material, the temperature employed, etc.

The preferred method of carrying out the process is to introduce methylene chloride, phenol and aqueous ammonia into an autoclave, the phenol being taken in considerable excess and the ammonia'also preferably being taken in some excess; heat the autoclave at a comparatively high temperature, say, a temperature of 180 6., and continue the operation until the reaction is complete.

according to conwhich not with the same readiness.

another chamber. The aqueous ammonium chloride is then passed into a still where it is treated with hydrated lime, producing aqueous calcium chloride and ammonia. The ammonia may be passed back to a storage tank and from there used again in the autoclave for practicing the process of producing the phenolic condensation product.

The fusible resin preferably is subjected to an operation whereby a portion of the excess 0 phenol is eliminated. This may be effected by boiling the resin or by blowing air through the heated resin. In this manner, ten er cent or more of the original amount 0 phenol employed may be removed. Thereafter, the resin may be mixed with a suitable active methylene body, preferably hexamethylenetetramine, or, if desired, formaldehyde, or formaldehyde and ammonia.

The amount of the methylene body thus introduced into the resin should be sufficient to give to the final mass about one methylene group to each phenolic group. This mass when subjected to heat will be converted to the final infusible and substantially insoluble phenolic condensation product known to the art. At a suitable stage, fibrous fillers or other fillers may be com ounded with the resin, if desired. In the usible and soluble stage, the resin may be dissolved in an a propriate solvent and used as. a varnis sufficient hexamethylenetetramine or other active methylene body being added to efiect the conversion to the final infusible and substantially insoluble state.

Any suitable phenolic body may be employed in the processi Phenol, the cresols and naphthols condense with equal readiness with methylene chloride in the presence of ammonia. The ethylidene and propylidenechlorides react in the same manner but Several hours, perhaps six to eight hours, are required to complete the reaction with ethylidene chloride under the conditions stated above; and, in the case of propylidene chloride, the reaction requires a period of more than twenty-four hours heating at 180 C. It seems to be the rule that the reactivit de creases as the size of the allryl radio e increases. While a temperature of 180 C. has been given as a suitable temperature for these condensations, lower temperatures may be used if desirable. For example, the condensation of methylene chloride with phenol in the presence of ammonia can be effected at a temperature of 100 C. in the course of 12 to '24 hours. The same applies to the condensation of. cresols with methylene chloride. If ethylidene or propylidene chloride be. used it is more practicable to use the higher temperature.

. The ordinary alkalies can not be used to replace ammonia. Indeed, if the ordinary alkalies be used in large amount when am monium hydroxide is present in theoretical -molecular proportions less than the theo-" retical amount of-resin will be obtained as a result oi the reaction.- As an illustration, one may take the following:

Phenol 9 mols.

Methylene chloride 6 mols.

SIodium hydroxide (30% solution), 12 mo s. s

Ammonium hydroxide 12 mols.

If these materials be heated at170 to 180 C. for 25 minutes, the reaction will be complete, that is, all. methylene chloride will have reacted. However, such reaction yields, only 90 to 95% of the theoretical quantity of resin. Thus, it appears that the ordinary alkali, while it does not prevent the reaction when ammonium hydroxide is present, nevertheless interferes with the reaction in some manner and prevents the full yield of.

resin. If instead of 12 mols. of ammonium hydroxide only 1 to 2 mols. are used the yield of resin amounts to only a few per cent of the theoretical yield. On the other hand, any suitable compound of ammonia, such as methyl-amine or am-' ,monlum carbonate, may be used in l1eu of ammonia. Also, any suitable phenolic body maybe employed, including phenol, the cre-* sols, and other, higher homologues. In the appended claims where the expression ammonia is used, it shouldbe understood to include. such compounds of ammonia as may serve as substitutes. y I

The foregoing detailedb description has been given for clearness f understanding only and no unnecessary limitations should be understood therefrom, but the appended claims should be construed as broadly as permissible in view of the prior art.

What we regard as new, anddesire to" secure by Letters Patent, is

1. The process of producing a phenolic condensation product which com rises: causing a reaction between an al ehyde dichloride, a phenoIic bOdy and ammonia, the ammonia being present in suificient quantity to combine with substantially all of the chlorine liberated in the reaction.

acting upon=a phenolicbody with an alde 2.'The process of producing a'phenolic condensationjproduct which comprises: re

chlorine; and separating the ammonium chlorid formed from the resin formed. 30

4. The process of producing a phenolic condensation product which comprises: causing a reaction between an aldehyde dichloride, a phenolic body and ammonium hydroxide, the ammonium hydroxidebeing a dilute solution and being present in sufficient quantity to combine with substan-.- tially all of the chlorine liberated in the reaction. Y

5. The process of producing a phenolic condensation product which comprises:

-mixing an aldehyde dichloride, a phenolic body and a solutionpf'ammonia' and subjecting the same to the action of heat and pressure. Y

6. The process of producing a phenolic condensation product which comprises: mixing an aldehyde dichloride, a. phenolic body and a solutionof ammonia; and subject-mg the same to the action of heat and pressure, the temperature employed being not substantially lower than C.

7. The process of producing a phenolic condensation product which comprises: heating an'aldehyde dichloride, a phenolicbody and a solution of ammonia, the phenolic body being taken in excess of the molecular proportions and the ammonia being taken in'excessof the molecular proportions; and separating the causing a reaction between methylene chloride, a henolic bodyfandammonia, the ammonia. ing presentin-suflicient quantity to combine with substantially all of the L chlorine of the methylene chloride. 9. The process of producing a phenolic condensation product which comprises:

causing a reaction between methylene chloride, a phenolic bodymand a soluiton of ammonia, the phenolic dy being taken in excess'of the molecular proportions'and heat being applied to influence the reaction; separating the ammonium chloride formed from the resin formed; introducing into the resin a sufiicient amount of an active methylene body to efiect conversion to a 1 1% c .meeeee final, infusible and substantially insoluble of the chlorine of the aldehyde dichloride; 1 state; and applying heat to effect eonverseparating the ammonium chloride from the sion, to the final state resin formed; recovering the ammonia from 10. The process of prgflucing a phenolic the ammonium chloride; and using the re 5 condensation proeiuct which comprises: covered ammonia to treat a fresh mixture causing a reaction between on aldehyde of phenolic body and aldehyde-dichloride 115 dichloride, e phenol-T10 body made ammonia, to produce a, phenolic condensation product. the: eonie being present in suficient CARNIE B. CARTER.

quantity to combine with substantially all ALBERT E. CGXE. 

